HU216904B - Process for structuring liquid nonionic surfactants prior to granulation process and that detergent compounds - Google Patents

Abstract

The present invention relates to a process for the preparation of a granular bleach detergent with a bulk density of at least 650 g / l, in the form of a monopolymer. . The invention further relates to detergent stone pellets produced by this process. ŕ

Description

This invention relates to a granular detergent detergent component having a bulk density of at least 650 g / l.

(a) by pumping the structuring grains containing a polymer into a liquid non-ionic surfactant which can be pumped into a premix; and

b) fine dispersion of the premix in powder form.

The process according to the invention is mainly liquid at room temperature and can therefore be used with mobile nonionic surfactants. Without a suitable structuring agent, the nonionic surfactant tends to seep out of the powder and soak the carton, causing a repulsive appearance. Although this can be avoided by using a smaller amount of nonionic surfactant in the formulation, or by using a surfactant with a higher pour point, this limits the formulation possibilities.

The use of nonionic surfactants in granular detergents has been widely discussed in the art. The following publications describe various methods for preparing granules of nonionic surfactants.

U.S. Patent No. 3,868,336 discloses the use of a powder mixture comprising perborate, tripolyphosphate, nonionic surfactant and polyvinyl alcohol. This premix is dry added to other detergent components.

British Patent No. 2137221 discloses a nonionic premix comprising dissolved polyvinylpyrrolidone (PVP) and a soil release polymer. The premix is sprayed onto an absorbent detergent carrier particle. PVP is used as a stabilizer in the soil removal polymer.

European Patent 0215 637 discloses sugars and sugar derivatives as structuring agents for spray-dried detergent powders. Although non-ionic surfactants may be present in such powders, they are used in relatively small amounts (e.g. 1.5 to 4.0% by weight in Examples 1-5). Further, the spray-dried powder has a low bulk density (324-574 g / liter).

EP 0513 824 describes a process for granulating a nonionic detergent and a surface coating agent having a particle size of less than 10 µm to produce a powder (10-60% by weight) having a nonionic surfactant content and a bulk density of 0.6-1. 2 g / ml. Polymers such as poly (ethylene glycol), polyvinyl alcohol, polyvinylpyrrolidone and carboxymethyl cellulose are disclosed (see page 13, lines 17-18). However, the description does not disclose the advantages of these polymers in structuring or thickening the nonionic surfactant.

International Patent Application No. 92 6160 describes a granular detergent composition (Example 14) which is prepared by fine dispersion in an Eirich mixer RVO2 containing N-methylglucosamide and a nonionic surfactant. in the presence of sodium carbonate and zeolite. There is no indication as to why polymers are used as structuring agents.

SUMMARY OF THE INVENTION One aspect of the present invention is to provide granular nonionic detergent agglomerates having a bulk density of at least 650 g / l which contain greater amounts of nonionic surfactants than previously known in the art, but do not impede the mobility of nonionic surfactants (i.e., ) which leaks out of the granules and soaks the carton.

This problem is avoided by structuring the nonionic surfactant prior to the dispersion and / or granulation process. This is accomplished by dissolving a structuring agent consisting of a polymeric material in the nonionic surfactant. Preferred structuring agents are polymers having more than one functional hydroxy group, in particular polyvinyl alcohols, polyhydroxyacrylic acid, polymers, and polymers such as polyvinylpyrrolidone and polyvinylpyridine. N-oxide) (VATO). Sugars, artificial sweeteners and derivatives thereof are useful components of the structuring agent.

It is a further object of the present invention to provide a process for introducing an adhesive into detergent granules while preserving their desired physical properties, such as good dispersibility, with good adhesion to the particles. If adhesives are present on or near the surface of the granules, they will have a negative effect on the dispersion properties. These materials also tend to gel upon contact with water, which prevents the granules from being dispensed well from the washing machine dispenser or from the laundry dispenser. The process of the present invention solves these problems by adding a tackifier to the nonionic surfactants which improves the surface properties of the granules.

Another object of the present invention is to provide high bulk density granular detergent components comprising nonionic surfactants and structuring agents.

The present invention relates to a granular detergent component or composition having a bulk density of at least 650 g / l, which comprises dissolving a polymer-containing structuring agent in a nonionic surfactant to form a pumpable premix and treating said premix with an effective amount of a powder. at a temperature of at least 350 mPas at a shear rate of 25 sec * ¹ . Preferred structuring agents include polymers having more than one functional hydroxyl group, in particular polyvinyl alcohols, polyhydroxy acrylic acid polymers and polymers such as polyvinylpyrrolidone and PVNO, and sugars.

EN 216 904 Β Artificial sweeteners and their derivatives. The premix is then processed to a granular detergent by a suitable process. Preferably, finely dispersed mixing, agglomeration or spraying of the premix onto a granular product is used.

Another object of the present invention is to provide components or compositions comprising nonionic surfactants and structuring agents.

The process according to the invention consists essentially of two steps. The first process step is to form a nonionic surfactant premix containing a structuring agent. The second process step is to process the surfactant premix in the form of a granular detergent which has the desired properties in terms of bulk density, scattering properties and storage properties.

The first step of the process of the present invention is to provide a structured, nonionic, surfactant premix. This premix contains two essential components as described below. These two components are the nonionic surfactant and the structuring agent. In the first step of the process, the structuring agent is dissolved in the nonionic surfactant.

The second step of the process is known to those skilled in the art in any technique by which granules can be formed. However, the most preferred technique for the present invention is to finely disperse the structured nonionic surfactant paste in the presence of powder. An example of this process is to pump or spray (spray) the surfactant paste into a high shear mixer. The high shear rate in the mixer distributes the surfactant paste into small droplets and distributes these droplets in and around the powder. The process is often referred to as "agglomeration".

Another example of this process is to spray the surfactant paste on a powder in a low shear (e.g., rotary drum) machine. In this case, the energy required to disperse the paste into fine droplets is provided by the spray valve and, in a low shear mixer, the droplets are absorbed on the powder surface or pores thereof. The preferred granulation methods are described in more detail below.

As used herein, the term "structuring" refers to thickening (increasing the viscosity) or increasing the pour point of a nonionic surfactant, or both. It is important for the present invention that the premix has a viscosity of greater than 350 mPas when measured at an operating temperature of 25 sec ^-1 shear.

By operating temperature is meant the temperature of the surfactant paste at which it is sprayed or dispersed during the granulation step of the process.

By "pumpable paste" is meant a paste having a viscosity of less than 25 seconds at a desired operating temperature of 25 sec ^-1 shear.

100,000 mPas. The paste preferably has a viscosity of less than 60,000 mPas, and more preferably less than 40,000 mPas.

Non-ionic surfactant

Suitable nonionic surfactants include condensation products of alkylene oxide groups (having hydrophilic properties) with an organic hydrophobic compound of aliphatic or alkyl aromatic nature. The length of the polyoxyalkylene group fused to any given hydrophobic group can be readily selected to provide a water-soluble compound having the desired ratio of hydrophilic to hydrophobic elements.

Particularly preferred nonionic surfactants for use in the present invention, such as polyethylene oxide condensates of alkyl phenols, such as about 6 to about 16 carbon atoms, linear or branched alkyl phenols, are about 4-25 moles of ethylene. condensation products of oxide / mol with alkylphenol.

Preferred nonionic materials are the condensation products of aliphatic alcohols having from 8 to 20 carbon atoms, linear or branched, with an average of 1-25 moles of ethylene oxide per mole of alcohol. Particularly preferred are the condensation products of alcohols having from about 9 to about 15 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol; and condensation products of propylene glycol with ethylene oxide. Most preferred are condensation products of alcohols having from about 12 to about 15 carbon atoms with an average of about 3 moles of ethylene oxide per mole of alcohol.

Many of the above-defined nonionic surfactants are those that are liquid at temperatures below 40 ° C (i.e., the pour point is below 40 ° C). The present invention is particularly applicable to such nonionic surfactants. Structuring agent

Although any structuring agent may be selected which increases the viscosity or "tack" or the cure temperature of the surfactant premix to the extent desired, it has been found that structuring agents containing at least one polymer are particularly preferred.

At least one component of the structuring agent components is a polymer having an average molecular weight of at least 2000, preferably at least 10,000.

One class of polymers that can be used as structuring agents for the purposes of the present invention are polymers containing at least one functional hydroxyl group, such as polyvinyl alcohols, polyethylene glycol and polyhydroxyacrylic acid polymers, and mixtures thereof, and derivatives thereof. . Other polymers that can be used as a structuring agent include polyvinylpyrrolidone, PVNO.

The structuring agent may also contain other components. Sugars, artificial sweeteners and their derivatives are one such group which has been found to be very advantageous.

Sugar derivatives form a very preferred group of structuring agents for use in the present invention.

EN 216 904 Β as poly (hydroxy-fatty acid amide) derivatives. Such derivatives may be prepared by reacting a fatty acid ester with an N-alkylpoly (hydroxyamine). A preferred amine for use in the present invention is N- (R 1) CH ₂ (CH ₂ O ₄ ) ₄ -CH ₂ OH, and the preferred ester is a C 10-20 fatty acid methyl ester. Most preferred is the reaction product of N-methylglucamine (an amyglucamine derivative) and a C 10-20 fatty acid methyl ester.

Methods for the production of polyhydroxy fatty acid amides are described in PCT International Patent Application WO 926073. This disclosure describes the preparation of polyhydroxy fatty acid amides in the presence of solvents. In a very preferred embodiment of the invention, N-methylglucamine is reacted with a C 10-20 methyl ester. It is also mentioned that the formulator of the granular detergent composition will find it suitable that the amidation reaction be a solvent such as alkoxylated, especially ethoxylated (EO 3-8), C 12-14 alcohols (see page 15, pages 22-27 of this specification). lines). This results directly in the nonionic surfactants preferred for the present invention, such as those containing N-methylglucamine and C12-C14 alcohols having an average of 3 ethoxylates per molecule.

Poly (hydroxy-fatty acid amides) are themselves surfactants during the washing process.

Other components which have been found to be effective as components of the structuring agent include phthalimide, paratoluenesulfonamide and maleimide.

The ratio of the nonionic surfactant to the structurant will vary according to which nonionic surfactant and which structurant is selected. Any ratio may be used in accordance with the present invention provided that a premix is prepared which has a viscosity of at least 350 mPas at an operating temperature of 25 sec ^-1 shear. In particular, a weight ratio of nonionic surfactant: structuring agent of 20: 1 to 1: 1, and preferably a weight ratio of 5: 1 to 2: 1, has been found to be suitable.

Under normal circumstances, the detergent components of the present invention may contain a variety of other ingredients and components known to those skilled in the art to perform the washing process. Several typical examples of such ingredients for use in detergent compositions are given below.

Granulation procedures

An important step of the present invention is the preparation of granules comprising a surfactant premix. One skilled in the art is familiar with a variety of methods for granulating surfactant pastes. One such method is spray drying of the slurry containing surfactant. However, this is not an advantageous process for the present invention because it does not generally produce a high bulk density powder and further processing is required to increase the bulk density. A more suitable process for the present invention is fine dispersion mixing or agglomeration. In this process, a relatively small particle size powder is mixed with a finely dispersed paste which causes the powder to adhere (or agglomerate). The result is a granular formulation having a particle size distribution in the range 250-1200 µm and a bulk density of at least 650 g / l. According to the present invention, the surfactant premix is used as a paste which is mixed with an effective amount of powder in a suitable mixer. The finely dispersed agitators suitable for mixing are described in more detail below. Any suitable powder may be selected for admixture with one or more of the components listed below which may be suitably treated in powder form. Powders consisting of zeolite, carbonate, silica, silicates, phosphates, citrates, citric acid and mixtures thereof are particularly preferred.

It has further been found that a particularly advantageous embodiment of the process of the invention is that water is sprayed onto the detergent granules after the granulation step. In this embodiment of the process according to the invention, at least one of the powders used must be anhydrous powder which may be wholly or partially hydrated upon contact with water. A similar procedure is described in British Patent No. 2,113,707. This specification describes a process for adding anhydrous powders such as phosphate, carbonate, borate or sulfate to a high shear mixer (a KG Schugi BLENDERAGGLOMERATOR ^R ) together with a liquid surfactant and water. The amount of water supplied is sufficient to completely hydrate the hydrated salts. The resulting agglomerates are fed to a high residence time, low shear mixer for complete hydration reaction.

In contrast, in the process of the present invention, it is very advantageous to feed the water into the low shear mixer after the agglomerates have formed. Without wishing to be bound by theory, it is believed that the addition of water to the mixture after the initial formation of the agglomerates contributes to the hydration of the surface of the agglomerates, leading to the desired physical properties.

In the most preferred embodiment of the process of the invention, anhydrous sodium carbonate or anhydrous sodium citrate or a mixture thereof is used. The anhydrous salts are agglomerated in the presence of a structured nonionic surfactant premix and water is sprayed onto the resulting agglomerate in a low shear mixer. The agglomerates are finally dried in a fluid bed dryer.

Another embodiment of the process of the present invention consists in preparing a granular detergent powder and spraying the surfactant premix onto this powder. The powder base may be prepared by any method known to those skilled in the art, such as powder

HU 216 904 Β by dry drying, granulation (including agglomeration). Preferably, a variety of processes are used to prepare the various components, and the components are then blended, for example, in a rotary drum mixer or low shear mixer. In a preferred embodiment of the process of the invention, the surfactant premix is sprayed onto the powder base in a rotary drum mixer or low shear mixer.

The apparatus for performing the fine dispersion mixing or granulation process of the present invention is the FUKAE ^R FS-G Series of Fukae Powtech Kogyo Co., Japan. This apparatus is essentially a container-shaped vessel with an upper opening, with a mixer having a substantially vertical axis near its bottom and a cutting device located on its side wall. The mixer and the shredder can be operated independently and at variable speeds. The container may be provided with a cooling jacket or, if necessary, a freezer.

Other similar apparatuses useful in the process of the present invention include DIOSNA ^R V series apparatus from Dierks und Söhne in Germany and PHARMA MATRIX ^R apparatus from TK Fielder Ltd. in England. Other mixing devices for use in the process of the present invention are believed to belong to the Fuji® VG-C series of Japanese company Fuji Sangyo Co.; and the Italian company Zanchetta &Co.'s ROTO ^R equipment.

Other suitable equipment may include the EIRICH ^R RV of Gustan Eirich, Hardheim, Germany; batch-mode and Baud KM continuous-mixing / agglomeration equipment of the FM series of Lödige Maschinenbau GmbH, Padembon, Germany; equipment by Drais Werke, Mannheim, Germany; and RT-25 by Winkworth Machinery Ltd., Berkshire, England.

FM-130-D-12 Littleford Mixer with Inner Cutting Edges and Cuisinat Foor Processor DCX-Plus with 19.7 cm Blades are two more examples of suitable mixing devices. Any other dispersion mixer and granulation mixer can be used with a residence time of between 0.1 and 10 minutes. An "turbine-type" impeller mixer with a plurality of blades on a single mixing shaft is preferred. The process according to the invention can be carried out batchwise or continuously. Further procedural steps

The components or compositions described above may be used directly or may be further processed. Conventional process steps include drying, cooling and / or treating the granulate with a finely divided dispersant. In addition, the granulate may be provided with other ingredients to provide a formulation suitable for the desired end use.

Any mixing or drying device (such as a fluid bed dryer) is suitable for this purpose.

When finely divided dispersing aids are used, the multi-purpose component may be zeolite, silica, talc, clay, or a mixture thereof.

preparations

Another object of the present invention is to provide detergent components containing a nonionic surfactant. For the purposes of the present invention, formulations having a bulk density greater than 650 g / l, containing from 10 to 50% by weight of a nonionic surfactant and from 5 to 30% by weight, of a structuring agent as listed above. The ratio of nonionic surfactant to structuring agent will vary according to which nonionic surfactant and which structuring agent is selected. Any such ratio may be selected provided that a premix having a viscosity of at least 350 mPas at the operating temperature and shear rate of 25 sec ^{-1 is} prepared. It is particularly appropriate that the typical weight ratio of nonionic surfactant to structuring grains be in the range of 20: 1 to 1: 1, preferably 5: 1-2: 1.

Other components useful in preparing the compositions of the present invention are described below.

Under normal circumstances, the detergent granule may optionally contain other components. Such components commonly used in detergents are described in more detail below. Anionic surfactants

Alkyl ester sulfonate surfactant

Alkyl ester sulfonate surfactants useful herein include linear esters of C8-C20 carboxylic acids (i.e., fatty acids) as disclosed in The Journal of the American Oil Chemists Society, Vol. 52, pp. 323-329. p. (1975) sulfonated with gaseous sulfur trioxide. Suitable starting materials include tallow, palm, and the like. natural oils from oil.

Preferred alkyl ester sulfonate surfactants that are particularly useful for washing purposes include

SHE

II

R ³ -CH-C-OR ⁴

Compounds of formula SO ₃ M wherein R ³ is a C 8-20 hydrocarbon group, preferably an alkyl group or a combination thereof,

R ⁴ is a C 1 -C 6 hydrocarbon group, preferably an alkyl group or a combination thereof, and M is a cation which forms a water-soluble salt with the alkyl ester sulfonate.

Suitable salt-forming cations include sodium, potassium, and lithium metal cations, as well as substituted or unsubstituted ammonium cations such as monoethanolamine, diethanolamine, and triethanolamine.

R ³ is preferably C 10 -C 16 alkyl and R ⁴ is methyl, ethyl or isopropyl;

HU 216 904 Β port. Particularly preferred are methyl ester sulfonates wherein R ³ is C 14 -C 16 alkyl.

Alkyl sulphate surfactants

Said alkyl sulfate surfactants in a ROSO ₃ M water-soluble salts or acids of the formula are those wherein:

Preferably R is a C 10 -C 29 hydrocarbon group, preferably an alkyl group or a C 10 -C 20 alkyl hydroxyalkyl group, and

M is hydrogen or a cation such as an alkali metal (e.g., sodium, potassium, lithium) or ammonium or substituted ammonium (e.g. methyl, dimethyl, trimethylammonium) or quaternary ammonium such as tetramethylammonium. or a dimethylpiperidinium cation or a quaternary ammonium cation derived from alkylamines such as ethylamine or a mixture thereof and the like.

At lower wash temperatures (e.g., below about 50 ° C), C12-16 alkyl chains are typically preferred and at higher (e.g., above 50 ° C) C16-18 alkyl chains are preferred.

Alkyl alkoxylated sulfate surfactants

The alkylalkoxylated sulfate surfactants in question are water-soluble salts or acids of the formula RO (A) _m SO ₃ M

R is an unsubstituted alkyl or hydroxyalkyl group containing from 10 to 24 carbon atoms, preferably a C 12-20 alkyl or hydroxyalkyl group, more preferably a C 12-18 alkyl or hydroxyalkyl group,

A is ethoxy or propoxy, m is greater than zero, typically about 0.5 to about 6, preferably 0.5 to 3, and

M is hydrogen or a cation which may be, for example, a metal cation (e.g., sodium, potassium, calcium, magnesium, etc.), ammonium or substituted ammonium cation.

Alkyl ethoxylated as well as alkyl propoxylated sulfates. Specific examples of substituted ammonium cations include methyl, dimethyl, trimethylammonium, dimethylpiperidinium cations, and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like. Examples of such surfactants include C12-C18 alkyl polyethoxylate (10) sulfate, C12-C18 E (1.0) M, C12-C18 alkyl polyethoxylate (2.25) sulfate, C12-C18 E (2.25M). ), C 12 -C 18 alkyl polyethoxylate (3,0) sulfate C 12 -C 18 E (3,0), and C 12 -C 18 alkyl polyethoxylate (4,0) sulfate C 12 -C 18 (4), 0) M, wherein M is a suitably selected sodium or potassium cation. Other anionic surfactants

Other anionic surfactants may also be used in the detergent compositions of the present invention. These may include soap salts (e.g., sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- or triethanolamine salts), C9-20 linear alkyl benzene sulfonates, C8-22 primary or secondary alkanesulfonates, 8 Sulfonated polycarboxylic acids obtained by sulfonation of pyrolysed products of C szén-C ol ol olefin sulfonates, alkaline earth metal citrates, such as those disclosed in British Patent 1,082,179, oxides); acylglycerol sulfonates, fatty oleylglycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as acyl isethionates, N-acyl taurates, alkyl succates sulfosuccinamates, sulfosuccinamate monoesters (especially C12-C18 saturated and unsaturated monoesters), sulfosuccinate diesters (especially C6-C14 saturated and unsaturated diesters), acyl sarcosinates, alkyl polysaccharide sulfates, polyglucoside sulfates, branched primary alkyl sulfates, alkyl poly (ethoxycarboxylates), such as RO (CH ₂ CH ₂ O) _k CH ₂ COO-M ⁺ , wherein k is from 0 to An integer of up to 10 and M is a cation forming a soluble salt. Resin acids and hydrogenated resin acids are also suitable, such as rosin (a yellow resin containing abietic anhydride), hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil.

Further examples are given by Schwartz, Perry and Berch:

Surface Active Agents and Detergents, c. I. and II. volume. A number of such detergents are also described in U.S. Patent No. 3,929,678 (column 23, line 58 to column 29, line 23), which is incorporated herein by reference.

When used, the detergent detergent compositions of the present invention typically contain from about 1% to about 40%, preferably from about 3% to about 20% by weight of such anionic surfactant.

Other surfactants

The detergent compositions of the present invention may contain, in addition to those described herein, other cationic, ampholytic, zwitterionic, and semi-polar and nonionic surfactants, such as the semi-polar, nonionic oxides described below.

Suitable cationic detergent surfactants for the detergent compositions of the present invention are those having a long chain hydrocarbon group. Such cationic surfactants include, for example, surfactant ammonium compounds such as alkyldimethylammonium halides and

R1R2R3R4N + X is a surfactant of the general formula wherein

R ¹ is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in its alkyl chain

Each of R ² , R ³ , R ⁴ is independently C 1-4 alkyl, C 1-4 hydroxyalkyl, benzyl 6

Or a group of the formula - (C ₂ H ₄ ) _X H wherein x is a number from 2 to 5 and X is an anion. At most one of R ² , R ³ and R ⁴ may be benzyl.

The preferred chain length of the R ¹ alkyl chain is 12 to 15 carbon atoms, especially when the alkyl group is derived from coconut or palm kernel oil, or is synthetically based on olefins or is an oxalcohol synthesis product. Preferred substituents R ² , R ³ and R ⁴ are methyl and hydroxyethyl groups, the X-anion being selected from the group consisting of halide, methosulfate, acetate and phosphate.

Suitable quaternary ammonium compounds for our purposes include:

coconut trimethylammonium chloride or bromide, coconut methyl dihydroxyethylammonium chloride or bromide, decyltriethylammonium chloride or bromide, decyldimethylhydroxyethylammonium chloride or - bromide,

C 12 -C 14 dimethylhydroxyethylammonium chloride or bromide, myristyl trimethylammonium methyl sulfate, lauryldimethylbenzylammonium chloride or bromide, laurylmethyl (ethenoxy) _4- ammonium chloride obsession

bromide.

The above water-soluble cationic components of the compositions of the present invention may exist in cationic form in 0.1% aqueous solution at pH 10.

Other cationic surfactants useful for our purposes are also described in U.S. Patent No. 4,228,044, which is incorporated herein by reference.

If such cationic surfactants are used in the detergent detergent compositions of the present invention, they will comprise from about 0% to about 25% by weight of the composition, preferably from about 3% to about 15% by weight.

Ampholytic surfactants may also be used in the detergent detergent compositions of the present invention. These surfactants are broadly described as aliphatic derivatives of secondary or tertiary amines or as aliphatic derivatives of heterocyclic secondary or tertiary amines in which the aliphatic group may be straight or branched. At least one of the aliphatic substituents contains about 8, typically from about 8 to about 18 carbon atoms, and at least one of them contains an anionic water-solubility group such as carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 (Col. 19, lines 18-35), which is incorporated herein by reference for examples of ampholytic surfactants.

When used in the detergent detergent compositions of the present invention, such ampholytic surfactants will typically be present in an amount of from 0 to 15%, preferably from about 1 to 10% by weight, based on the total weight of the composition.

For detergent compositions, zwitterionic surfactants are also suitable. These surfactants can be described in a broad sense as secondary and tertiary amine derivatives, heterocyclic secondary and tertiary amine derivatives or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. For examples of zwitterionic surfactants, see U.S. Patent 3,929,678 (Column 19, line 38 to column 22, line 48), which is incorporated herein by reference.

Where such zwitterionic surfactants are used in the detergent detergent compositions of the present invention, they will typically be present in an amount of from about 0% to about 15%, preferably from about 1% to about 10%.

Semi-polar, nonionic surfactants are a special class of nonionic surfactants that include water-soluble amine oxides having one alkyl moiety of about 10 to about 18 carbon atoms and two alkyl or hydroxyalkyl groups of from about 1 to about 3 carbon atoms. They include; or include water-soluble phospho-oxides containing one alkyl moiety of about 10 to about 18 carbon atoms and two alkyl or hydroxyalkyl groups of from about 1 to about 3 carbon atoms.

Semipolar, nonionic detergent surfactants include:

SHE

An amine oxide surfactant of the formula R ³ (OR ⁴ ) x N (R 5) _{2 in} which

R ³ is alkyl, hydroxyalkyl or alkylphenyl of about 8 to 22 carbon atoms or a mixture thereof,

R ⁴ is an alkylene or hydroxyalkylene group having about 2 to 3 carbon atoms or a mixture thereof, and

Each R ⁵ substituent is a C 1 -C 3 alkyl or hydroxyalkyl group or a polyethylene oxide group having about 1 to 3 ethylene oxide groups.

The ^R5 groups are linked to form a ring structure with each other through an oxygen or sulfur atom.

Here, the amine oxide surfactants are in particular composed of C 10 -C 18 alkyldimethylamine oxides and C 8 -C 12 alkoxyethyl dihydroxyethylamine oxides.

When used in the detergent detergent compositions of the present invention, such semipolar nonionic surfactants may be present in an amount of from 0 to about 15% by weight, preferably from 1 to 10% by weight of the composition.

Constructive and other components, as appropriate

Sodium aluminum silicate can take many forms. One example is a

Na ₂ [(AlO ₂ ) _z (SiO ₂ ) _y ] .H ₂ O is an ion-exchange crystalline aluminosilicate wherein z and y are at least about 6, and z has a molar ratio of about 1.0 to about 0.4, and z is about 10-264.

HU 216 904 Β

The general formula of amorphous hydrated aluminum silicate materials for this purpose

M _z (zA10 ₂ .ySi0 ₂ ) where

M is sodium, potassium, ammonium or substituted ammonium, z is about 0.5 to 2, and y is 1, said material having a magnesium ion exchange capacity of at least about 50 mg equivalent calcium carbonate hardness per gram of anhydrous aluminum silicate. Approximately (1-10) is preferred. 10 ” ¹⁰ m Hydrated Sodium Zeolite A.

Aluminum silicate ion-exchange building materials are in a hydrated form and, when crystalline, may contain from about 10% to about 28% by weight of water and, when amorphous, may contain even greater amounts of water. Such preferred crystalline aluminosilicate ion exchange materials contain from about 18% to about 22% water by weight in their crystal matrix. The crystalline aluminosilicate ion exchange materials are further characterized by a particle diameter of about 0.1 to about 10 µm. Amorphous materials often have a particle size smaller than, for example, 0.01 µm or less. Preferred ion-exchange materials have a particle diameter of about 0.2 to about 4 µm. By "particle diameter" is meant herein the weight average particle size of a given ion exchange material as determined by a conventional analytical method such as a scanning electron microscope. The crystalline aluminosilicate ion exchange agents discussed herein are further characterized by their calcium ion exchange ability, which is generally at least about 200 mg calcium carbonate equivalent water hardness / g aluminum silicate, calculated on an anhydrous basis, and generally 300 mg equivalents / g. mg equivalent / g. The aluminum silicate ion exchange materials in question are further characterized by their calcium ion exchange rate, which is at least about 9 Ca ⁺⁺ mg / l / min / g / g / l aluminum silicate (on an anhydrous basis) and generally about 9-27 mg / l. liter / min / gram / liter on a calcium ion basis. Optimal for forming purposes the calcium ion exchange rate of aluminum silicate is at least 18 mg / liter / min / gram / liter.

The amorphous aluminum silicate ion exchange materials have a Mg ⁺⁺ ion exchange capacity of at least 50 mg equivalent CaCO ₃ / g (12 mg Mg ++ / g) and a Mg ⁺⁺ ion exchange rate of at least about 4.5 mg / l / min / g / l. Amorphous materials do not exhibit noticeable diffraction when examined with Cu radiation (0.154 nm units).

Aluminum silicate ion exchange materials useful in the practice of the present invention are commercially available. They may be crystalline or amorphous, may be naturally occurring or synthetic aluminum silicates. The preparation of aluminum silicate ion exchange materials is disclosed in U.S. Patent No. 3,985,669, which is incorporated herein by reference. Preferred synthetic crystalline aluminosilicate ion exchange materials suitable for our purposes are commercially available as Zeolite A, Zeolite B, Zeolite M and Zeolit X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula

Na _{] 2} [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] .xH ₂ O, where x is about 20-30, in particular about 27, and has a particle size of less than about 5 µm.

Other substances known for use in these components and compositions may also be used according to the invention.

The granular detergents of the present invention may contain neutral or basic salts having a pH of 7 or more in solution, which may be inorganic or organic salts. The molding salt helps to ensure that the detergent granules have the desired density and density. While some of the salts are inert, many of these also help to develop detergent properties in the wash solution.

Neutral water-soluble salts include, for example, alkali metal, ammonium and substituted ammonium chlorides, fluorides and sulfates. Alkali metal salts, especially sodium salts, are preferred. Sodium sulfate is a particularly preferred salt which is typically used in detergent granules. Citric acid and in general other organic or inorganic acids may be used in the granular detergents of the present invention as long as they are chemically compatible with the other components of the agglomerate formulation.

Other water-soluble salts that may be used include substances commonly known as detergent builders. They are generally selected from various water-soluble alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carboxylic acids, silicates, borates and polyhydroxysulfonates. The above alkali metal salts, particularly sodium salts, are preferred.

Specific examples of inorganic phosphate forming agents are sodium and potassium tripolyphosphate, pyrophosphate, polymer metaphosphate having a degree of polymerization of about 6 to 21, and orthophosphate. Polyphosphate molding agents include, for example, sodium and potassium salts of ethylene diphosphonic acid, sodium and potassium salts of ethane-1-hydroxy-1,1-diphosphonic acid, and sodium and potassium salts of ethane-1,2,2-triphosphonic acid. Other phosphorous molding materials are disclosed in 3 159581; 3213030; 3422021; 3422 137; U.S. Patent Nos. 3,400,176; and 3,400,148, which are incorporated herein by reference.

Non-phosphorus-containing inorganic molding materials include, for example, sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate and sodium and potassium silicates having a molar ratio of SiO _{2 to} alkali metal oxide of about 0.5 to 4.0, preferably 1.0 to 2.4.

As mentioned above, in preferred embodiments of the detergents of the present invention, zeolites, carbonates, silica, silicates, citrates, phosphates, perborates, and starch processing aids are normally used as powders. polymers

Various organic polymers can be used, some of which have detergent properties for8

EN 216 904 Β Activators, anti-foaming agents, anti-foaming agents, anti-fading and anti-corrosive preparations, soil suspending agents, soil release agents, fillers, optical brighteners, disinfectants, pH adjusting agents, non-forming alkalizers and enzymes, hydrotropic agents, .

Examples also have a glazing role. Such polymers include sodium carboxy (lower) alkyl celluloses, such as sodium carboxymethyl cellulose and sodium hydroxypropyl cellulose, polyvinyl alcohols, which are often some polyvinyl alcohol. acetate), polyacrylamides, polyacrylates and various copolymers such as maleic and acrylic acid copolymers. The molecular weight of such polymers varies over a wide range, but is generally in the range of 2000 to 100,000.

Polymeric polycarboxylate molding materials are disclosed in U.S. Patent No. 3,308,067. Such materials include water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, humic acid, aconitic acid and methylenemalonic acid.

Other components, if applicable

Other components commonly used in detergent compositions may also be used in the components and compositions of the present invention. These include dyes, bleaches and bleaches. In our examples, the following abbreviations are used:

10 C25E3: C12-C15 ethoxylate with an average of 3 ethoxy groups per molecule, GA: N-methyl glucamide, C25AS: C 12 -C 15 alkyl sulfate, 15 G45AS: C 14 -C 15 alkyl sulfate, C25AE3S: C12-C15 alkyl ethoxysulfate having an average of 3 ethoxy groups per molecule, PVP: poly (vinylpyrrolidone), 20 PVNO: poly (vinylpyridine-N-oxide).

Table I

Example number 1 2 3 4 5 6 7 C25E3 80 75 67 67 46 46 46 PVP 20 25 33 33 PVNO 13 13 13 Lactose 11 dextrose 11 saccharose 11 Water 30 30 30 Operating temperature (° C) 30 3 15 15 20 20 20 Viscosity (mPas) 900 1300 2000 2000 23,000 23,000 23,000 8 9 10 THE C25E3 75 67 86 97.5 GA 12.5 11 PVP 22 14 2.5 PVNO 12.5 Operating temperature (° C) 40 40 20 20 Viscosity (mPas) 24000 15000 380 50

Example 1

The C25E3 / PVP paste as defined in Table I was sprayed into a LOEDIGE CB ^R mixer at 1120 kg / h at 30 ° C. However, Zeolite A was added to the mixer at a rate of 1340 kg / h and anhydrous carbonate was added at a rate of 1340 kg / h.

The paste premix was dispersed, and the premix and powder mixed with high intensity in a Loedig mixer. The residence time was approximately 8 seconds.

The resulting mixture was fed to a LOEDIGE KM ^R mixer and agglomerates were formed. The two high speed chopping knives in the front of the LOEDIGE KM ^R mixer prevented the formation of large, oversized agglome55.

In the second half of the Loedige KM ^R mixer, water was sprayed onto the agglomerate at a rate of 225 kg / h to help hydrate the carbonate in the agglomerate.

HU 216 904 Β

After spraying the water, a mixture of zeolite and silica was fed at a rate of 160 kg / h.

The agglomerate drained from the mixer was then passed through a fluid bed cooling / settler.

The resulting agglomerate had excellent physical properties (including excellent dispersibility) and was also physically stable under forced storage conditions.

Example 2

The procedure of Example 1 was repeated using the components listed in Table I.

Example 3

The procedure described in Example 1 was repeated

Using the components listed in Table I so that the operating temperature of the paste premixes was 15 ° C.

Example 4

The procedure of Example 3 was repeated with the components listed in Table I, but Zeolite A was replaced with anhydrous citrate and the rate of water addition was increased to 190 kg / h.

Example 5

The C25E3 / PVNO / lactose paste as defined in Table I was sprayed into a LOEDIGE CB ^R mixer at 1400 kg / h at 20 ° C. Simultaneously, Zeolite A was added to the mixer at a rate of 1200 kg / h and anhydrous carbonate was added at a rate of 1200 kg / h.

The remainder of the process was carried out as described in Example 1, and the agglomerates were sprayed with water at a rate of 200 kg / h.

6-10. example

The procedure of Example 5 was repeated using the components listed in Table I.

2-10. For each of Examples 1 to 4, a high dispersibility granule product was obtained which appeared to be physically stable under forced storage conditions.

Comparative Example A

The procedure of Example 5 was repeated and the components listed in Table I were used. Due to the low viscosity of the surfactant premix, it was not possible to obtain granules of appropriate particle size and physical properties.

Claims (12)

PATENT CLAIMS A process for the preparation of a granular detergent detergent component having a bulk density of at least 650 g / l by: (a) pumping structuring grains comprising a polymer into a liquid nonionic surfactant to be pumped into a premix; and b) dispersing the fine with the premix poranyaggal, characterized in that the fine dispersing of the premix is carried out at a temperature of at least 350 mPa.s viscosity at 25 sec ¹ shear rate. 2. The process of claim 1, wherein the structuring agent comprises more than one functional hydroxyl group. 3. A process according to claim 1 or 2, characterized in that a structuring agent is used which comprises at least one component such as polyvinylpyrrolidone, polyvinylpyridine N-oxide, vinyl alcohol), a poly (hydroxyacrylic acid) polymer or a mixture thereof. A process according to claim 2 or 3, characterized in that a structuring agent is used which comprises at least one component such as dextrose, lactose, sucrose, saccharin or a saccharin derivative, polyhydroxy fatty acid amide. 5. A process according to any one of claims 1 to 3, characterized in that a structuring agent is used which contains at least one component such as phthalimide, para-toluenesulfamide, maleimide or a mixture thereof. 6. A process according to any one of claims 1 to 3, wherein the structuring agent is a polymer having a molecular weight of at least 2000. 7. A process according to any one of claims 1 to 3, characterized in that a granular laundry detergent component is present which contains at least 10% by weight of a nonionic surfactant. 8. Process according to any one of claims 1 to 3, characterized in that in process step b) zeolite, silica, carbonate, silicate, sulphate, phosphate, citrate, citric acid or a mixture thereof is used as a powder. A process for the preparation of a granular detergent detergent component having a bulk density of at least 650 g / l (a) providing a pumpable premix by dissolving a structuring eye in a nonionic surfactant; and b) finely dispersing the premix with a powder, wherein the premix is finely dispersed at a shear rate of 25 seconds at a temperature of at least 350 mPas and at least a portion of the powder is in a hydrated form; and spraying water with the resulting product. 10. A detergent component having a bulk density of at least 650 g / l which, with the usual detergent additives (i) 10 to 50% by weight of a liquid nonionic surfactant; (ii) 5 to 30% by weight of a structuring agent such as sugar, artificial sweetener, polyvinyl alcohol, poly (hydroxyacrylic acid) polymer or derivative, polyvinyl pyrrolidone), polyvinylpyridine N-oxide, phthalimide, paratoluenesulfamide, maleimide or ke10. EN 216 904 Β and the weight ratio of components (i) and (ii) is from 10: 1 to 1: 1. The detergent component according to claim 10, wherein the nonionic surfactant has a chain length of 8 to 20 carbon atoms and has an average ethoxylated alcohol of 1 to 25, preferably 2 to 10 ethoxy groups per molecule. The detergent component of claim 11, wherein the nonionic surfactant is below 40 ° C 5 at liquid temperature.